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WO2018194159A1 - Électrode de dispositif électrochimique et son procédé de production, dispositif électrochimique et composition d'électrolyte polymère - Google Patents

Électrode de dispositif électrochimique et son procédé de production, dispositif électrochimique et composition d'électrolyte polymère Download PDF

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WO2018194159A1
WO2018194159A1 PCT/JP2018/016318 JP2018016318W WO2018194159A1 WO 2018194159 A1 WO2018194159 A1 WO 2018194159A1 JP 2018016318 W JP2018016318 W JP 2018016318W WO 2018194159 A1 WO2018194159 A1 WO 2018194159A1
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Prior art keywords
electrode
salt
polymer
electrolyte
positive electrode
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PCT/JP2018/016318
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English (en)
Japanese (ja)
Inventor
祐介 瀬良
秀之 小川
紘揮 三國
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日立化成株式会社
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Publication date
Priority claimed from PCT/JP2017/016079 external-priority patent/WO2018193627A1/fr
Priority claimed from PCT/JP2017/016084 external-priority patent/WO2018193630A1/fr
Application filed by 日立化成株式会社 filed Critical 日立化成株式会社
Priority to CN202310599693.XA priority Critical patent/CN116404107A/zh
Priority to US16/606,334 priority patent/US11462767B2/en
Priority to JP2019513702A priority patent/JP7163909B2/ja
Priority to CN201880026140.2A priority patent/CN110537274B/zh
Priority to EP18787019.1A priority patent/EP3614469A4/fr
Priority to KR1020197029920A priority patent/KR102595311B1/ko
Publication of WO2018194159A1 publication Critical patent/WO2018194159A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0045—Room temperature molten salts comprising at least one organic ion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an electrode for an electrochemical device and a method for producing the same, an electrochemical device, and a polymer electrolyte composition.
  • Lithium ion secondary batteries are energy devices having a high energy density, and are used for portable devices such as notebook computers and mobile phones, and power sources for electric vehicles, taking advantage of their characteristics.
  • a separator is sandwiched between a positive electrode and a negative electrode, and the separator is impregnated with an organic electrolyte.
  • the organic electrolyte since the organic electrolyte is flammable, it may ignite when an abnormality occurs and the temperature of the battery rises. It is important to improve safety when starting to increase energy density and size in lithium ion secondary batteries, and it is required to avoid situations such as ignition from the configuration of lithium ion secondary batteries. Yes.
  • Patent Document 1 discloses a method of adding an inorganic solid electrolyte to an electrode mixture layer in a lithium ion battery.
  • the inorganic solid electrolyte used in the method described in Patent Document 1 has poor flexibility, and it is difficult to change the shape in accordance with the shape of the voids in the electrode mixture layer in the positive electrode and the negative electrode. Characteristics may not be obtained.
  • the amount of the inorganic solid electrolyte added is increased in order to improve the interface forming property, the ratio of the electrode active material in the electrode relatively decreases, so that the battery characteristics tend to decrease.
  • the present invention has been made in view of the above circumstances, and an electrode for an electrochemical device capable of enhancing battery characteristics even when a battery is produced by adding a solid electrolyte to an electrode mixture layer and its electrode
  • An object is to provide a manufacturing method.
  • an object of this invention is to provide the electrochemical device using such an electrode for electrochemical devices.
  • an object of this invention is to provide the polymer electrolyte composition which can improve the ionic conductivity of an electrode mixture layer.
  • a first aspect of the present invention comprises an electrode current collector and an electrode mixture layer provided on at least one main surface of the electrode current collector, the electrode mixture layer comprising an electrode active material,
  • a polymer having a structural unit represented by the following general formula (1) hereinafter sometimes simply referred to as “polymer”
  • electrolyte salt lithium salt, sodium salt, calcium salt, and magnesium salt 1 type of electrolyte salt
  • molten salt molten salt having a melting point of 250 ° C. or less
  • the electrode for an electrochemical device of the first aspect of the present invention since a good interface is formed between the electrode active material and the polymer in the electrode mixture layer, a solid electrolyte is added to the electrode mixture layer. Even when the battery is manufactured, the battery characteristics can be improved.
  • the anion of the electrolyte salt is selected from the group consisting of PF 6 ⁇ , BF 4 ⁇ , N (FSO 2 ) 2 ⁇ , N (CF 3 SO 2 ) 2 ⁇ , B (C 2 O 4 ) 2 ⁇ , and ClO 4 ⁇ . It may be at least one selected.
  • the electrolyte salt may be a lithium salt.
  • the content of the molten salt may be 10 to 80% by mass based on the total amount of the polymer, the electrolyte salt, and the molten salt.
  • Electrode device electrode may be a positive electrode. That is, the electrode current collector may be a positive electrode current collector, the electrode mixture layer may be a positive electrode mixture layer, and the electrode active material may be a positive electrode active material.
  • the electrode for an electrochemical device may be a negative electrode. That is, the electrode current collector may be a negative electrode current collector, the electrode mixture layer may be a negative electrode mixture layer, and the electrode active material may be a negative electrode active material.
  • the negative electrode active material may contain graphite. When the negative electrode active material contains graphite, the electrolyte salt preferably contains LiN (FSO 2 ) 2 .
  • the second aspect of the present invention is an electrochemical device comprising the above-described electrode for an electrochemical device.
  • the electrochemical device may be a secondary battery.
  • a step of preparing an electrode precursor in which an electrode active material layer containing an electrode active material is provided on at least one main surface of an electrode current collector, and an electrode active material of the electrode precursor
  • the layer has a polymer having a structural unit represented by the following general formula (1), at least one electrolyte salt selected from the group consisting of a lithium salt, a sodium salt, a calcium salt, and a magnesium salt, and a melting point of 250.
  • the anion of the electrolyte salt is selected from the group consisting of PF 6 ⁇ , BF 4 ⁇ , N (FSO 2 ) 2 ⁇ , N (CF 3 SO 2 ) 2 ⁇ , B (C 2 O 4 ) 2 ⁇ , and ClO 4 ⁇ . It may be at least one selected.
  • the content of the molten salt may be 10 to 80% by mass based on the total amount of the polymer, the electrolyte salt, and the molten salt.
  • the dispersion medium may contain acetone.
  • the mass ratio of the dispersion medium content to the polymer content (“dispersion medium content” / “polymer content”) may be 6 or less.
  • At least one electrolyte selected from the group consisting of a polymer having a structural unit represented by the following general formula (1), and a lithium salt, a sodium salt, a calcium salt, and a magnesium salt.
  • a polymer electrolyte composition comprising a salt and a molten salt having a melting point of 250 ° C. or lower.
  • the anion of the electrolyte salt is selected from the group consisting of PF 6 ⁇ , BF 4 ⁇ , N (FSO 2 ) 2 ⁇ , N (CF 3 SO 2 ) 2 ⁇ , B (C 2 O 4 ) 2 ⁇ , and ClO 4 ⁇ . It may be at least one selected.
  • the electrolyte salt may be a lithium salt.
  • the content of the molten salt may be 10 to 80% by mass based on the total amount of the polymer, the electrolyte salt, and the molten salt.
  • the polymer electrolyte composition may further contain a dispersion medium.
  • the dispersion medium may contain acetone.
  • the mass ratio of the content of the dispersion medium to the content of the polymer may be 6 or less.
  • an electrode for an electrochemical device and a method for producing the same that can improve battery characteristics even when a battery is produced by adding a solid electrolyte to an electrode mixture layer.
  • the electrochemical device using such an electrode for electrochemical devices is provided.
  • the polymer electrolyte composition which can improve the ionic conductivity of an electrode mixture layer is provided.
  • FIG. 1 is a perspective view showing an electrochemical device according to a first embodiment. It is a disassembled perspective view which shows the electrode group of the electrochemical device shown in FIG. 2A is a cross-sectional view taken along the line II of FIG. 2 for illustrating an electrode for an electrochemical device (positive electrode) according to one embodiment, and FIG. 2B is for an electrochemical device according to another embodiment. It is a schematic cross section which shows an electrode (positive electrode). 2A is a cross-sectional view taken along the line II-II in FIG. 2 for illustrating an electrode for an electrochemical device (negative electrode) according to one embodiment, and FIG. 2B is for an electrochemical device according to another embodiment. It is a schematic cross section which shows an electrode (negative electrode).
  • FIG. 3A is a cross-sectional view taken along the line III-III of FIG. 2 for explaining an electrode for an electrochemical device (bipolar electrode) according to another embodiment
  • FIG. It is a schematic cross section which shows the electrode for devices (bipolar electrode).
  • A) is a scanning electron microscope image of the positive electrode produced in Example 1-1
  • (b) is an image showing the distribution of cobalt by energy dispersive X-ray analysis in the positive electrode shown in FIG. 7 (a).
  • (C) is the image which shows distribution of sulfur by the energy dispersive X-ray analysis in the positive electrode shown to Fig.7 (a).
  • Example 6 is a graph showing battery performance evaluation of the secondary batteries produced in Example 1-1 and Comparative Example 1-1.
  • A is a scanning electron microscope image of the positive electrode produced in Example 3-1, and (b) is a scanning electron microscope image of the positive electrode produced in Example 3-2.
  • A) is a scanning electron microscope image of the positive electrode produced in Example 3-3, and (b) is a scanning electron microscope image of the positive electrode produced in Example 3-4.
  • a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
  • electrode means a positive electrode or a negative electrode.
  • electrode current collector an electrode mixture layer, an electrode active material, an electrode active material layer, and an electrode precursor.
  • FIG. 1 is a perspective view showing an electrochemical device according to the first embodiment.
  • the electrochemical device may be a secondary battery.
  • aspects of the secondary battery will be described.
  • the secondary battery 1 includes an electrode group 2 composed of an electrode for an electrochemical device and an electrolyte layer, and a bag-shaped battery exterior body 3 that houses the electrode group 2.
  • the electrode for an electrochemical device may be a positive electrode or a negative electrode.
  • the electrode for an electrochemical device (positive electrode and negative electrode) is provided with a positive electrode current collecting tab 4 and a negative electrode current collecting tab 5, respectively.
  • the positive electrode current collecting tab 4 and the negative electrode current collecting tab 5 protrude from the inside of the battery outer package 3 to the outside so that the positive electrode and the negative electrode can be electrically connected to the outside of the secondary battery 1, respectively.
  • the battery outer package 3 may be formed of, for example, a laminate film.
  • the laminate film may be a laminate film in which a resin film such as a polyethylene terephthalate (PET) film, a metal foil such as aluminum, copper, and stainless steel, and a sealant layer such as polypropylene are laminated in this order.
  • PET polyethylene terephthalate
  • metal foil such as aluminum, copper, and stainless steel
  • sealant layer such as polypropylene
  • FIG. 2 is an exploded perspective view showing an embodiment of the electrode group 2 in the secondary battery 1 shown in FIG.
  • the electrode group 2 ⁇ / b> A includes a positive electrode 6, an electrolyte layer 7, and a negative electrode 8 in this order.
  • the positive electrode 6 includes a positive electrode current collector 9 and a positive electrode mixture layer 10 provided on at least one main surface of the positive electrode current collector 9.
  • the positive electrode current collector 9 is provided with a positive electrode current collector tab 4.
  • the negative electrode 8 includes a negative electrode current collector 11 and a negative electrode mixture layer 12 provided on at least one main surface of the negative electrode current collector 11.
  • the negative electrode current collector 11 is provided with a negative electrode current collector tab 5.
  • FIG. 3A is a cross-sectional view taken along the line II of FIG.
  • the positive electrode 6 (first electrode for electrochemical device 13A) includes a positive electrode current collector 9 and a positive electrode composite provided on at least one main surface of the positive electrode current collector 9.
  • the agent layer 10 is provided.
  • FIG. 3B is a schematic cross-sectional view showing a first electrode for an electrochemical device according to another embodiment.
  • the first electrochemical device electrode 13B includes a positive electrode current collector 9, a positive electrode mixture layer 10, and an electrolyte layer 7 in this order.
  • the first electrochemical device electrode 13 ⁇ / b> A includes a positive electrode current collector 9.
  • the positive electrode current collector 9 may be formed of aluminum, stainless steel, titanium, or the like.
  • the positive electrode current collector 9 may be, for example, an aluminum perforated foil having a hole diameter of 0.1 to 10 mm, an expanded metal, a foamed metal plate, or the like.
  • the positive electrode current collector 9 may be formed of any material as long as it does not cause changes such as dissolution and oxidation during use of the battery, and its shape, manufacturing method, etc. Not limited.
  • the thickness of the positive electrode current collector 9 may be 1 ⁇ m or more, 5 ⁇ m or more, or 10 ⁇ m or more.
  • the thickness of the positive electrode current collector 9 may be 100 ⁇ m or less, 50 ⁇ m or less, or 20 ⁇ m or less.
  • the first electrochemical device electrode 13 ⁇ / b> A includes the positive electrode mixture layer 10.
  • the positive electrode mixture layer 10 contains a positive electrode active material, a specific polymer, a specific electrolyte salt, and a specific molten salt.
  • the positive electrode mixture layer 10 contains a positive electrode active material.
  • the positive electrode active material may be, for example, a lithium transition metal compound such as a lithium transition metal oxide or a lithium transition metal phosphate.
  • the lithium transition metal oxide may be lithium manganate, lithium nickelate, lithium cobaltate, or the like.
  • Lithium transition metal oxide is a part of transition metals such as Mn, Ni, Co, etc. contained in lithium manganate, lithium nickelate, lithium cobaltate, etc., one or more other transition metals, or A lithium transition metal oxide substituted with a metal element (typical element) such as Mg or Al may also be used. That is, the lithium transition metal oxide may be a compound represented by LiM 1 O 2 or LiM 1 O 4 (M 1 includes at least one transition metal).
  • lithium transition metal oxides are Li (Co 1/3 Ni 1/3 Mn 1/3 ) O 2 , LiNi 1/2 Mn 1/2 O 2 , LiNi 1/2 Mn 3/2 O. It may be 4 etc.
  • the lithium transition metal oxide may be a compound represented by the following formula (A) from the viewpoint of further improving the energy density.
  • Lithium transition metal phosphates are LiFePO 4 , LiMnPO 4 , LiMn x M 3 1-x PO 4 (0.3 ⁇ x ⁇ 1, M 3 is Fe, Ni, Co, Ti, Cu, Zn, Mg, and Or at least one element selected from the group consisting of Zr).
  • the content of the positive electrode active material may be 70% by mass or more, 80% by mass or more, or 90% by mass or more based on the total amount of the positive electrode mixture layer.
  • the content of the positive electrode active material may be 99% by mass or less based on the total amount of the positive electrode mixture layer.
  • the positive electrode mixture layer 10 contains a polymer having a structural unit represented by the following general formula (1).
  • X ⁇ represents a counter anion.
  • X ⁇ for example, BF 4 ⁇ (tetrafluoroborate anion), PF 6 ⁇ (hexafluorophosphate anion), N (FSO 2 ) 2 ⁇ (bis (fluorosulfonyl) imide anion, [FSI ] -), N (CF 3 SO 2) 2 - ( bis (trifluoromethanesulfonyl) imide anion, [TFSI] -), C (SO 2 F) 3 - ( tris (fluorosulfonyl) carbanions, [f3C] - ), B (C 2 O 4 ) 2 ⁇ (bisoxalate borate anion, [BOB] ⁇ ), BF 3 (CF 3 ) ⁇ , BF 3 (C 2 F 5 ) ⁇ , BF 3 (C 3 F 7 ) ⁇ , BF 3 (C 4 F 9 ) ⁇ , C
  • X ⁇ is preferably at least one selected from the group consisting of BF 4 ⁇ , PF 6 ⁇ , [FSI] ⁇ , [TFSI] ⁇ , and [f3C] ⁇ , more preferably [TFSI] ⁇ . Or [FSI] ⁇ .
  • the viscosity average molecular weight Mv (g ⁇ mol ⁇ 1 ) of the polymer having the structural unit represented by the general formula (1) is not particularly limited, but is preferably 1.0 ⁇ 10 4 or more, more preferably 1.0 ⁇ . 10 5 or more. Further, the viscosity average molecular weight of the polymer is preferably 5.0 ⁇ 10 6 or less, more preferably 1.0 ⁇ 10 6 or less.
  • the “viscosity average molecular weight” can be evaluated by a viscosity method which is a general measurement method. For example, from the intrinsic viscosity [ ⁇ ] measured based on JIS K 7367-3: 1999. Can be calculated.
  • the polymer having the structural unit represented by the general formula (1) is preferably a polymer consisting only of the structural unit represented by the general formula (1), that is, a homopolymer, from the viewpoint of ion conductivity.
  • the polymer having the structural unit represented by the general formula (1) may be a polymer represented by the following general formula (2).
  • n 300 to 4000
  • Y ⁇ represents a counter anion.
  • Y ⁇ those similar to those exemplified for X ⁇ can be used.
  • N is 300 or more, preferably 400 or more, more preferably 500 or more. Moreover, it is 4000 or less, preferably 3500 or less, more preferably 3000 or less. N is 300 to 4000, preferably 400 to 3500, and more preferably 500 to 3000.
  • the production method of the polymer having the structural unit represented by the general formula (1) is not particularly limited, and for example, the production method described in Journal of Power Sources 2009, 188, 558-563 can be used.
  • poly (diallyldimethylammonium) chloride [P (DADMA)] [Cl]
  • P (DADMA)] [Cl] poly (diallyldimethylammonium) chloride
  • a commercially available product can be used as it is.
  • Li [TFSI] is dissolved in deionized water to prepare an aqueous solution containing Li [TFSI].
  • the molar ratio of Li [TFSI] to [P (DADMA)] [Cl] was 1.2 to 2.0.
  • the two aqueous solutions are mixed and stirred for 2 to 8 hours to precipitate a solid, and the obtained solid is collected by filtration.
  • a polymer having a structural unit represented by the general formula (1) ([P (DADMA)] [TFSI]) can be obtained by washing the solid with deionized water and vacuum drying for 12 to 48 hours. it can.
  • the content of the polymer having the structural unit represented by the general formula (1) may be 5 to 50% by mass based on the total amount of the polymer, the electrolyte salt described later, and the molten salt described later.
  • the content of the polymer is more preferably 8% by mass or more, further preferably 15% by mass or more, based on the total amount of the polymer, the electrolyte salt, and the molten salt.
  • the content of the polymer is more preferably 35% by mass or less, still more preferably 25% by mass or less, based on the total amount of the polymer, the electrolyte salt, and the molten salt.
  • the positive electrode mixture layer 10 contains at least one electrolyte salt selected from the group consisting of a lithium salt, a sodium salt, a magnesium salt, and a calcium salt.
  • the electrolyte salt one used as an electrolyte salt of an electrolyte solution for a normal ion battery can be used.
  • the anion of the electrolyte salt includes halide ions (I ⁇ , Cl ⁇ , Br ⁇ etc.), SCN ⁇ , BF 4 ⁇ , BF 3 (CF 3 ) ⁇ , BF 3 (C 2 F 5 ) ⁇ , BF 3 (C 3 F 7 ) ⁇ , BF 3 (C 4 F 9 ) ⁇ , PF 6 ⁇ , ClO 4 ⁇ , SbF 6 ⁇ , [FSI] ⁇ , [TFSI] ⁇ , N (C 2 F 5 SO 2 ) 2 ⁇ , BPh 4 ⁇ , B (C 2 H 4 O 2 ) 2 ⁇ , [f3C] ⁇ , C (CF 3 SO 2 ) 3 ⁇ , CF 3 COO ⁇ , CF 3 SO 2 O ⁇ , C 6 F 5 SO 2 O -, [BOB] -, RCOO - (.
  • R is an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a naphthyl group), or the like.
  • the anion of the electrolyte salt is preferably at least one selected from the group consisting of PF 6 ⁇ , BF 4 ⁇ , [FSI] ⁇ , [TFSI] ⁇ , [BOB] ⁇ , and ClO 4 ⁇ .
  • [TFSI] ⁇ or [FSI] ⁇ is more preferable, and [FSI] ⁇ is more preferable.
  • Lithium salts include LiPF 6 , LiBF 4 , Li [FSI], Li [TFSI], Li [f 3 C], Li [BOB], LiClO 4 , LiBF 3 (CF 3 ), LiBF 3 (C 2 F 5 ), LiBF 3 (C 3 F 7 ), LiBF 3 (C 4 F 9 ), LiC (SO 2 CF 3 ) 3 , LiCF 3 SO 2 O, LiCF 3 COO, LiRCOO (R is an alkyl group having 1 to 4 carbon atoms, A phenyl group or a naphthyl group). These may be used alone or in combination of two or more.
  • Sodium salts include NaPF 6 , NaBF 4 , Na [FSI], Na [TFSI], Na [f 3 C], Na [BOB], NaClO 4 , NaBF 3 (CF 3 ), NaBF 3 (C 2 F 5 ), NaBF 3 (C 3 F 7 ), NaBF 3 (C 4 F 9 ), NaC (SO 2 CF 3 ) 3 , NaCF 3 SO 2 O, NaCF 3 COO, NaRCOO (R is an alkyl group having 1 to 4 carbon atoms, A phenyl group or a naphthyl group). These may be used alone or in combination of two or more.
  • Magnesium salts are Mg (PF 6 ) 2 , Mg (BF 4 ) 2 , Mg [FSI] 2 , Mg [TFSI] 2 , Mg [f 3 C] 2 , Mg [BOB] 2 , Mg (ClO 4 ) 2 , Mg [BF 3 (CF 3 ) 3 ] 2 , Mg [BF 3 (C 2 F 5 )] 2 , Mg [BF 3 (C 3 F 7 )] 2 , Mg [BF 3 (C 4 F 9 )] 2 , Mg [C (SO 2 CF 3 ) 3 ] 2 , Mg (CF 3 SO 2 O) 2 , Mg (CF 3 COO) 2 , Mg (RCOO) 2 (R is an alkyl group having 1 to 4 carbon atoms, phenyl Or a naphthyl group). These may be used alone or in combination of two or more.
  • the calcium salts are Ca (PF 6 ) 2 , Ca (BF 4 ) 2 , Ca [FSI] 2 , Ca [TFSI] 2 , Ca [f3C] 2 , Ca [BOB] 2 , Ca (ClO 4 ) 2 , Ca [BF 3 (CF 3 ) 3 ] 2 , Ca [BF 3 (C 2 F 5 )] 2 , Ca [BF 3 (C 3 F 7 )] 2 , Ca [BF 3 (C 4 F 9 )] 2 , Ca [C (SO 2 CF 3 ) 3 ] 2 , Ca (CF 3 SO 2 O) 2 , Ca (CF 3 COO) 2 , Ca (RCOO) 2 (R is an alkyl group having 1 to 4 carbon atoms, phenyl Or a naphthyl group). These may be used alone or in combination of two or more.
  • a lithium salt more preferably LiPF 6 , LiBF 4 , Li [FSI], Li [TFSI], Li [f3C], Li [BOB], And at least one selected from the group consisting of LiClO 4 , more preferably Li [TFSI] or Li [FSI], particularly preferably Li [FSI].
  • the mass ratio of the electrolyte salt to the polymer having the structural unit represented by the general formula (1) is not particularly limited. Preferably it is 0.1 or more, More preferably, it is 0.15 or more, More preferably, it is 0.2 or more.
  • the mass ratio is preferably 1.0 or less, more preferably 0.9 or less, and still more preferably 0.8 or less. When the mass ratio is 0.1 or more, the ion carrier concentration is sufficient, and the ionic conductivity tends to be further improved. When the mass ratio is 1.0 or less, the flexibility of the electrolyte tends to be further improved.
  • the content of the electrolyte salt may be 5 to 30% by mass based on the total amount of the polymer, the electrolyte salt, and the molten salt described later.
  • the content of the electrolyte salt is more preferably 10% by mass or more based on the total amount of the polymer, the electrolyte salt, and the molten salt. Further, the content of the molten salt is more preferably 25% by mass or less based on the total amount of the polymer, the electrolyte salt, and the molten salt.
  • the content of the electrolyte salt is not particularly limited, but may be 0.1% by mass or more based on the total amount of the positive electrode mixture layer.
  • the content of the electrolyte salt may be 15% by mass or less based on the total amount of the positive electrode mixture layer.
  • the positive electrode mixture layer 10 contains a molten salt having a melting point of 250 ° C. or lower.
  • the molten salt is composed of a cation and an anion.
  • a normal ionic liquid or a plastic crystal can be used without any particular limitation.
  • ionic liquid means a molten salt that is liquid at 30 ° C., that is, a molten salt having a melting point of 30 ° C. or less
  • plastic crystal is a molten salt that is solid at 30 ° C. It means a salt, that is, a molten salt having a melting point higher than 30 ° C.
  • the ionic liquid can be used without particular limitation as long as it is a molten salt that is liquid at 30 ° C.
  • a molten salt that is liquid at 30 ° C.
  • [TFSI] -, or [F3C] - a combination of a include those which are liquid at 30 ° C..
  • the melting point of the ionic liquid is not particularly limited, but is preferably 25 ° C. or less, more preferably 10 ° C. or less, and further preferably 0 ° C. or less. When the melting point is 25 ° C. or lower, the ionic conductivity tends not to decrease even at room temperature (for example, 25 ° C.) or lower.
  • the lower limit of the melting point of the ionic liquid is not particularly limited, but may be ⁇ 150 ° C. or higher, ⁇ 120 ° C. or higher, or ⁇ 90 ° C. or higher.
  • the plastic crystal can be used without particular limitation as long as it is a solid at 30 ° C. and is a molten salt having a melting point of 250 ° C. or lower.
  • [TFSI] -, or [F3C] - a combination of, those of the solid at 30 ° C..
  • the cation of the molten salt is preferably [EMI] + , [DEME] + , [Py12] + , or [Py13] + , more preferably [EMI] + from the viewpoint of ionic conductivity.
  • the anion of the molten salt is preferably [FSI] ⁇ or [TFSI] ⁇ , more preferably [FSI] ⁇ from the viewpoint of ionic conductivity.
  • the molten salt is [EMI] [FSI], [DEME] [FSI], [Py12] [FSI], [Py13] [FSI], [EMI] [TFSI], [DEME] [ [TFSI], [Py12] [TFSI], or [Py13] [TFSI] is preferably included, and [EMI] [FSI] is more preferably included.
  • the melting point of the plastic crystal is 250 ° C. or less, preferably 200 ° C. or less, more preferably 150 ° C. or less, and further preferably 100 ° C. or less.
  • the ionic conductivity tends to increase.
  • fusing point of molten salt is not restrict
  • the content of the molten salt may be 10 to 80% by mass based on the total amount of the polymer, the electrolyte salt, and the molten salt.
  • the content of the molten salt is more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 40% by mass or more based on the total amount of the polymer, the electrolyte salt, and the molten salt.
  • the content of the molten salt is more preferably 75% by mass or less, still more preferably 70% by mass or less, based on the total amount of the polymer, the electrolyte salt, and the molten salt.
  • the content of the molten salt is not particularly limited, but may be 0.5% by mass or more based on the total amount of the positive electrode mixture layer.
  • the content of the molten salt may be 25% by mass or less based on the total amount of the positive electrode mixture layer.
  • the positive electrode mixture layer 10 may further contain a conductive agent, a binder and the like.
  • the conductive agent may be carbon black, graphite, carbon fiber, carbon nanotube, acetylene black or the like.
  • the content of the conductive agent may be 1 to 15% by mass based on the total amount of the positive electrode mixture layer.
  • the binder is a resin such as polyvinylidene fluoride, polyacrylonitrile, styrene / butadiene rubber, carboxymethyl cellulose, fluorine rubber, ethylene / propylene rubber, polyacrylic acid, polyimide, polyamide; copolymer resin having these resins as a main skeleton ( For example, it may be a polyvinylidene fluoride-hexafluoropropylene copolymer).
  • the content of the binder may be 1 to 15% by mass based on the total amount of the positive electrode mixture layer.
  • the thickness of the positive electrode mixture layer 10 is not particularly limited, but may be 10 ⁇ m or more, 20 ⁇ m or more, or 30 ⁇ m or more.
  • the thickness of the positive electrode mixture layer 10 may be 100 ⁇ m or less, 80 ⁇ m or less, or 60 ⁇ m or less.
  • the mixture density of the positive electrode mixture layer 10 may be 1 g / cm 3 or more.
  • the electrolyte layer 7 contains a solid electrolyte, an electrolyte salt, and a molten salt.
  • the electrolyte layer 7 what formed the electrolyte composition containing the said component in the sheet form (electrolyte sheet
  • solid electrolytes examples include polymer electrolytes and inorganic solid electrolytes.
  • the polymer electrolyte and the inorganic solid electrolyte are not particularly limited, and those used as a polymer electrolyte and an inorganic solid electrolyte for a normal ion battery can be used.
  • the polymer having the structural unit represented by the general formula (1) described above may have properties as a polymer electrolyte. Therefore, the polymer can be suitably used as a polymer electrolyte.
  • the inorganic solid electrolyte may be Li 7 La 3 Zr 2 O 12 (LLZ) or the like.
  • the electrolyte salt and molten salt may be the same as the electrolyte salt and molten salt contained in the positive electrode mixture layer described above.
  • the electrolyte composition may further contain an additive having lithium salt dissociation ability such as borate ester and aluminate ester, if necessary.
  • an additive having lithium salt dissociation ability such as borate ester and aluminate ester, if necessary.
  • the electrolyte sheet is formed by forming an electrolyte composition containing oxide particles, a binder, an electrolyte salt, and an ionic liquid into a sheet shape. It may be.
  • the oxide particles are, for example, inorganic oxide particles.
  • the inorganic oxide is an inorganic oxide containing, for example, Li, Mg, Al, Si, Ca, Ti, Zr, La, Na, K, Ba, Sr, V, Nb, B, Ge and the like as constituent elements. Good.
  • the oxide particles are at least one particle selected from the group consisting of SiO 2 , Al 2 O 3 , AlOOH, MgO, CaO, ZrO 2 , TiO 2 , Li 7 La 3 Zr 2 O 12 , and BaTiO 3. May be. Since the oxide particles have polarity, it is possible to promote dissociation of the electrolyte in the electrolyte layer 7 and improve battery characteristics.
  • the binder, electrolyte salt, and ionic liquid may be the same as the binder, electrolyte salt, and ionic liquid contained in the positive electrode mixture layer described above.
  • the thickness of the electrolyte layer 7 may be 5 to 200 ⁇ m from the viewpoint of increasing strength and improving safety.
  • FIG. 4A is a cross-sectional view taken along the line II-II in FIG.
  • the negative electrode 8 (second electrochemical device electrode 14A) includes a negative electrode current collector 11 and a negative electrode composite provided on at least one main surface of the negative electrode current collector 11. And an agent layer 12.
  • FIG. 4B is a schematic cross-sectional view showing a second electrode for an electrochemical device according to another embodiment.
  • the second electrode for electrochemical device 14B includes a negative electrode current collector 11, a negative electrode mixture layer 12, and an electrolyte layer 7 in this order. Since the electrolyte layer 7 is the same as the electrolyte layer 7 in the first electrode for electrochemical devices described above, the description thereof is omitted below.
  • the second electrochemical device electrode 14 ⁇ / b> A includes the negative electrode current collector 11.
  • the negative electrode current collector 11 may be formed of copper, stainless steel, titanium, nickel, or the like. Specifically, the negative electrode current collector 11 may be a rolled copper foil, a copper perforated foil having holes having a hole diameter of 0.1 to 10 mm, an expanded metal, a foamed metal plate, or the like.
  • the negative electrode current collector 11 may be formed of any material other than the above, and its shape, manufacturing method, and the like are not limited.
  • the thickness of the negative electrode current collector 11 may be 1 ⁇ m or more, 5 ⁇ m or more, or 10 ⁇ m or more.
  • the thickness of the negative electrode current collector 11 may be 100 ⁇ m or less, 50 ⁇ m or less, or 20 ⁇ m or less.
  • the second electrochemical device electrode 14 ⁇ / b> A includes the negative electrode mixture layer 12.
  • the negative electrode mixture layer 12 contains a negative electrode active material, a specific polymer, a specific electrolyte salt, and a specific molten salt.
  • the negative electrode mixture layer 12 contains a negative electrode active material. What is used as a negative electrode active material of the field
  • the negative electrode active material include lithium metal, lithium alloy, metal compound, carbon material, metal complex, and organic polymer compound. These may be used alone or in combination of two or more.
  • the negative electrode active material is preferably a carbon material. Examples of the carbon material include graphite such as natural graphite (flaky graphite, etc.), artificial graphite, carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black, amorphous carbon, Examples thereof include carbon fiber.
  • the negative electrode active material preferably contains graphite.
  • the content of the negative electrode active material may be 60% by mass or more, 65% by mass or more, or 70% by mass or more based on the total amount of the negative electrode mixture layer.
  • the content of the negative electrode active material may be 99% by mass or less, 95% by mass or less, or 90% by mass or less based on the total amount of the negative electrode mixture layer.
  • the negative electrode mixture layer 12 is selected from the group consisting of a polymer having a structural unit represented by the general formula (1) contained in the positive electrode mixture layer 10 and a lithium salt, sodium salt, calcium salt, and magnesium salt. At least one electrolyte salt and a molten salt having a melting point of 250 ° C. or lower. These contents are the same as those of the positive electrode mixture layer 10.
  • the electrolyte salt preferably contains Li [FSI].
  • the battery characteristics of the obtained secondary battery tend to be further improved.
  • the negative electrode mixture layer 12 may further contain a conductive agent, a binder and the like contained in the positive electrode mixture layer 10 described above. These contents are the same as those of the positive electrode mixture layer 10.
  • the thickness of the negative electrode mixture layer 12 is not particularly limited, but may be 10 ⁇ m or more, 15 ⁇ m or more, or 20 ⁇ m or more.
  • the thickness of the negative electrode mixture layer 12 may be 50 ⁇ m or less, 45 ⁇ m or less, or 40 ⁇ m or less.
  • the mixture density of the negative electrode mixture layer 12 may be 1 g / cm 3 or more.
  • the manufacturing method of the secondary battery 1 includes a first step of manufacturing the first electrochemical device electrode 13A (positive electrode 6), and a second electrochemical device electrode 14A (negative electrode 8). A third step of providing an electrolyte layer 7 between the first electrochemical device electrode 13A (positive electrode 6) and the second electrochemical device electrode 14A (negative electrode 8); .
  • a positive electrode active material layer containing a positive electrode active material is provided on at least one main surface of the positive electrode current collector.
  • a step of preparing a positive electrode precursor, a polymer having a structural unit represented by the general formula (1) in the positive electrode active material layer of the positive electrode precursor, and a group consisting of lithium salt, sodium salt, calcium salt, and magnesium salt A step of adding a slurry containing at least one electrolyte salt selected from the group, a molten salt having a melting point of 250 ° C.
  • the positive electrode mixture layer can be composed of an electrode active material, a polymer, an electrolyte salt, and a molten salt.
  • the positive electrode active material layer in the positive electrode precursor is prepared, for example, by preparing a slurry for forming a positive electrode active material layer in which a material containing a positive electrode active material, a conductive agent, a binder or the like is dispersed in a dispersion medium, and the positive electrode active material layer forming slurry.
  • a dispersion medium is not particularly limited, but may be water, an aqueous solvent such as a mixed solvent of alcohol and water, or an organic solvent such as N-methyl-2-pyrrolidone.
  • a slurry (a slurry for forming a positive electrode mixture layer) in which a material containing a polymer, an electrolyte salt, and a molten salt is dispersed in a dispersion medium is prepared, and the slurry is added to the positive electrode active material layer.
  • the method for adding the slurry is not particularly limited, and examples thereof include dripping, coating, and printing.
  • the dispersion medium is not particularly limited as long as it dissolves the polymer, but may be acetone, ethyl methyl ketone, ⁇ -butyrolactone, or the like. Among these, it is preferable that a dispersion medium contains acetone.
  • the content of the polymer, the content of the electrolyte salt, and the content of the molten salt relative to the total amount of the polymer, the electrolyte salt, and the molten salt in the slurry are the same as those of the polymer, electrolyte salt, and molten salt in the positive electrode mixture layer 10 described above. It may be the same as the polymer content, the electrolyte salt content, and the molten salt content relative to the total amount.
  • the mass ratio of the content of the dispersion medium to the content of the polymer may be 6 or less.
  • the mass ratio of the content of the dispersion medium to the content of the polymer is more preferably 5.5 or less, and even more preferably 5 or less.
  • the mass ratio of the content of the dispersion medium to the content of the polymer is 6 or less, the polymer filling property of the positive electrode mixture layer can be further improved, and better ionic conductivity tends to be obtained.
  • the lower limit value of the mass ratio of the dispersion medium content to the polymer content is not particularly limited, and may be, for example, 0.1 or more, 0.5 or more, 1 or more, or 2 or more.
  • volatile components are removed from the slurry added to the positive electrode active material layer to form the positive electrode mixture layer 10.
  • the method for removing the volatile component is not particularly limited, and can be performed by a commonly used method.
  • the second electrochemical device electrode 14A (negative electrode 8) in the second step can be produced by the same manufacturing method as the first electrochemical device electrode 13A (positive electrode 6) in the first step described above. it can. That is, the manufacturing method of the second electrode for electrochemical device 14A (negative electrode 8) prepares a negative electrode precursor in which a negative electrode active material layer containing a negative electrode active material is provided on at least one main surface of a negative electrode current collector.
  • At least selected from the group consisting of a polymer having a structural unit represented by the general formula (1) and a lithium salt, sodium salt, calcium salt, and magnesium salt in the negative electrode active material layer of the negative electrode precursor A step of adding a slurry containing one type of electrolyte salt, a molten salt having a melting point of 250 ° C. or less, and a dispersion medium; and removing a volatile component from the slurry added to the negative electrode active material layer; Forming an agent layer. Since the volatile component (dispersion medium) is removed, the negative electrode mixture layer can be composed of an electrode active material, a polymer, an electrolyte salt, and a molten salt.
  • the electrolyte layer 7 is at least one of the positive electrode mixture layer 10 side of the first electrochemical device electrode 13A (positive electrode 6) and the negative electrode mixture layer 12 side of the second electrochemical device electrode 14A (negative electrode 8). One is formed by coating. The electrolyte layer 7 is applied to both the positive electrode mixture layer 10 side of the first electrochemical device electrode 13A (positive electrode 6) and the negative electrode mixture layer 12 side of the second electrochemical device electrode 14A (negative electrode 8). May be formed. In this case, for example, the positive electrode 6 provided with the electrolyte layer 7 (that is, the first electrochemical device electrode 13B) and the negative electrode 8 provided with the electrolyte layer 7 (that is, the second electrochemical device electrode 14B). ) Are stacked such that the electrolyte layers 7 are in contact with each other, whereby the secondary battery 1 can be manufactured.
  • the electrolyte layer 7 is obtained by kneading the material used for the electrolyte layer 7 and dispersing it in a dispersion medium to obtain an electrolyte sheet forming slurry. And can be prepared by coating on a substrate and removing the dispersion medium.
  • the dispersion medium may be an organic solvent such as acetone, ethyl methyl ketone, ⁇ -butyrolactone, N-methyl-2-pyrrolidone.
  • the first electrochemical device electrode 13A (positive electrode 6), the electrolyte layer 7, and the second electrochemical device electrode 14A (negative electrode 8) are laminated by, for example, lamination.
  • the secondary battery 1 can be manufactured.
  • the electrolyte layer 7 is on the positive electrode mixture layer 10 side of the first electrochemical device electrode 13A (positive electrode 6) and on the negative electrode mixture layer 12 side of the second electrochemical device electrode 14A (negative electrode 8).
  • the positive electrode current collector 9, the positive electrode mixture layer 10, the electrolyte layer 7, the negative electrode mixture layer 12, and the negative electrode current collector 11 are stacked in this order.
  • the method for forming the electrolyte layer 7 on the positive electrode mixture layer 10 of the positive electrode 6 is, for example, by dispersing the material used for the electrolyte layer 7 in a dispersion medium.
  • An example is a method in which after the slurry for forming an electrolyte layer is obtained, the slurry for forming an electrolyte layer is applied onto the positive electrode mixture layer 10 using an applicator.
  • the dispersion medium may be an organic solvent such as acetone, ethyl methyl ketone, ⁇ -butyrolactone, N-methyl-2-pyrrolidone.
  • the electrolyte salt may be dissolved in the molten salt in advance and then dispersed in the dispersion medium together with other materials.
  • the method for forming the electrolyte layer 7 on the negative electrode mixture layer 12 of the negative electrode 8 (that is, the method for producing the second electrochemical device electrode 14B) is to form the electrolyte layer 7 on the positive electrode mixture layer 10 of the positive electrode 6. It may be similar to the method.
  • FIG. 5 is an exploded perspective view showing an electrode group of the secondary battery according to the second embodiment.
  • the secondary battery in the second embodiment is different from the secondary battery in the first embodiment in that the electrode group 2 ⁇ / b> B further includes a bipolar electrode 15. That is, the electrode group 2B includes the positive electrode 6, the first electrolyte layer 7, the bipolar electrode 15, the second electrolyte layer 7, and the negative electrode 8 in this order.
  • the bipolar electrode 15 is provided on the surface of the bipolar electrode current collector 16, the positive electrode mixture layer 10 provided on the surface of the bipolar electrode current collector 16 on the negative electrode 8 side, and the surface of the bipolar electrode current collector 16 on the positive electrode 6 side.
  • the negative electrode mixture layer 12 is provided.
  • FIG. 6A is a cross-sectional view taken along line III-III in FIG.
  • the bipolar electrode 15 constitutes a third electrochemical device electrode. That is, as shown in FIG. 6A, the third electrode 17 ⁇ / b> A for electrochemical devices includes a bipolar electrode current collector 16 and a positive electrode mixture layer provided on one surface of the bipolar electrode current collector 16. 10 and a negative electrode mixture layer 12 provided on the other surface of the bipolar electrode current collector 16.
  • FIG. 6B is a schematic cross-sectional view showing a third electrode for an electrochemical device (bipolar electrode member) according to another embodiment.
  • the third electrode for electrochemical device 17B includes a bipolar electrode current collector 16, and a positive electrode mixture layer 10 provided on one surface of the bipolar electrode current collector 16.
  • a second electrolyte layer 7 provided on the opposite side of the positive electrode mixture layer 10 from the bipolar electrode current collector 16, a negative electrode mixture layer 12 provided on the other surface of the bipolar electrode current collector 16, And a first electrolyte layer 7 provided on the opposite side of the negative electrode mixture layer 12 from the bipolar electrode current collector 16.
  • the bipolar electrode current collector 16 may be aluminum, stainless steel, titanium or the like, or may be a clad material formed by rolling and joining aluminum and copper or stainless steel and copper.
  • the first electrolyte layer 7 and the second electrolyte layer 7 may be the same or different from each other.
  • the polymer electrolyte composition includes a polymer having a structural unit represented by the general formula (1), at least one electrolyte salt selected from the group consisting of a lithium salt, a sodium salt, a calcium salt, and a magnesium salt, and a melting point And a molten salt having a temperature of 250 ° C. or lower.
  • the polymer electrolyte composition may further contain a dispersion medium.
  • the polymer, electrolyte salt, and molten salt may be the same as those exemplified in the polymer, electrolyte salt, and molten salt in the positive electrode mixture layer 10 described above.
  • the content of the polymer, the content of the electrolyte salt, and the content of the molten salt relative to the total amount of the polymer, the electrolyte salt, and the molten salt are the total amount of the polymer, the electrolyte salt, and the molten salt in the positive electrode mixture layer 10 described above.
  • the content may be the same as the numerical values exemplified for the polymer content, the electrolyte salt content, and the molten salt content.
  • the dispersion medium may be the same as the dispersion medium exemplified in the slurry (the slurry for forming the positive electrode mixture layer) in the first step for producing the first electrode for electrochemical device 13A (positive electrode 6).
  • the mass ratio of the content of the dispersion medium to the content of the polymer is the mass ratio of the content of the dispersion medium to the content of the polymer in the first step for producing the first electrode for electrochemical device 13A (positive electrode 6). It may be the same as the exemplified numerical value.
  • This positive electrode active material layer forming slurry was applied to both surfaces (both main surfaces) on a positive electrode current collector (a 20 ⁇ m thick aluminum foil), dried at 120 ° C., rolled, and coated on one side at 60 g / m. 2.
  • a positive electrode active material layer having a mixture density of 2.3 g / cm 3 was formed to prepare a positive electrode precursor.
  • This slurry for forming a negative electrode active material layer was applied to both sides of a negative electrode current collector (aluminum foil having a thickness of 20 ⁇ m), dried at 120 ° C. and rolled, and the coating amount on one side was 67 g / m 2 .
  • a negative electrode active material layer of 8 g / cm 3 was formed to prepare a negative electrode precursor.
  • the mass ratio of the content of the dispersion medium to the content of the polymer of the slurry A was 3. Further, 2 parts by mass of Li [TFSI] as an electrolyte salt, 10 parts by mass of [Py12] [TFSI] as a molten salt, and 16 parts by mass of acetone as a dispersion medium are added to 8 parts by mass of the obtained polymer. Stirring was performed to obtain slurry B (slurry for forming an electrolyte sheet).
  • Slurry B was dropped on a SUS plate having a diameter of 16 mm and dried at 40 ° C. for 2 hours to volatilize acetone. Then, it dried under reduced pressure of 1.0 ⁇ 10 4 Pa or less (0.1 atm or less) at 60 ° C. for 10 hours to obtain an electrolyte sheet having a thickness of 400 ⁇ m.
  • Example 1-1 Preparation of positive electrode> Slurry A was added to the positive electrode active material layer of the positive electrode precursor prepared above by a doctor blade method with a gap of 200 ⁇ m. Then, using a vacuum desiccator, 0.05 MPa pressure reduction and atmospheric pressure release were repeated 10 times to remove volatile components to produce a positive electrode mixture layer, and a positive electrode provided with a positive electrode mixture layer was obtained.
  • Slurry A was added to the negative electrode active material layer of the negative electrode precursor prepared above by a doctor blade method with a gap of 200 ⁇ m. Then, using a vacuum desiccator, 0.05 MPa pressure reduction and atmospheric pressure release were repeated 10 times to remove volatile components to produce a negative electrode mixture layer, and a negative electrode provided with a negative electrode mixture layer was obtained.
  • Slurry B was applied to the positive electrode mixture layer of the obtained positive electrode by a doctor blade method with a gap of 250 ⁇ m.
  • a vacuum desiccator 0.05 MPa pressure reduction and atmospheric pressure release were repeated 10 times, and vacuum drying was performed at 60 ° C. for 12 hours to obtain a positive electrode having an electrolyte layer with a thickness of 30 ⁇ m on the positive electrode mixture layer.
  • a negative electrode having an electrolyte layer with a thickness of 30 ⁇ m was obtained on the negative electrode mixture layer of the negative electrode.
  • the positive electrode and negative electrode having the electrolyte layer prepared above were punched out to ⁇ 15 mm in order to produce a coin-type battery.
  • the positive electrode and the negative electrode were overlapped and placed in a CR2032-type coin cell container so that the electrolyte layers were in contact with each other.
  • the obtained laminated body was sealed by caulking the upper part of the battery container via an insulating gasket, whereby the secondary battery of Example 1 was obtained.
  • battery preparation was performed in the glove box of argon atmosphere.
  • FIG. 7A is a cross-sectional image of one location with the positive electrode produced in Example 1, taken with a scanning electron microscope (SEM).
  • the positive electrode includes a positive electrode current collector 30 and a positive electrode mixture layer 20 provided on at least one main surface of the positive electrode current collector 30.
  • FIGS. 7B and 7C The results of surface analysis (element mapping) at the location shown in FIG. 7A are shown in FIGS. 7B and 7C.
  • Surface analysis was performed by energy dispersive X-ray analysis (SEM-EDX) attached to the SEM.
  • the pale (white) spot in FIG. 7B is a spot where cobalt is present.
  • Cobalt is derived from Li (Co 1/3 Ni 1/3 Mn 1/3 ) O 2 which is a positive electrode active material.
  • the pale (white) spot in FIG. 7C is a spot where sulfur is present.
  • Sulfur is derived from [TFSI] of [P (DADMA)] [TFSI], Li [TFSI], and [Py12] [TFSI].
  • components such as a polymer are uniformly dispersed in the positive electrode material, suggesting that an interface is formed between the polymer and other components and the positive electrode material.
  • Battery performance was evaluated using the secondary battery produced by the above method. Using a charge / discharge device (Toyo System Co., Ltd., trade name: TOSCAT-3200), charge / discharge measurement was performed at 50 ° C. and 0.05C. C represents “current value [A] / design theoretical capacity [Ah]”, and 1 C represents a current value for fully charging or discharging the battery in one hour. The results are shown in Table 1. It can be said that the larger the value of the discharge capacity, the better the battery characteristics.
  • FIG. 8 is a graph showing the battery performance evaluation of the secondary batteries produced in Example 1 and Comparative Example 1.
  • the secondary battery of Example 1 was found to have a discharge capacity approximately twice that of the secondary battery of Comparative Example 1 and excellent battery characteristics. From these results, it was confirmed that the electrode for an electrochemical device of the present invention can enhance battery characteristics even when a battery is produced by adding a solid electrolyte to the electrode mixture layer.
  • This positive electrode active material layer-forming slurry is applied to the main surface of the positive electrode current collector (aluminum foil having a thickness of 20 ⁇ m), dried at 120 ° C., rolled, and coated on one side at 120 g / m 2 .
  • a positive electrode active material layer of 2.7 g / cm 3 was formed to prepare a positive electrode precursor.
  • carbon nanotube conductive agent, trade name: VGCF, fiber diameter 150 nm (manufacturer catalog value), Showa Denko KK) 0.4 part by mass
  • This negative electrode active material layer forming slurry is applied to the main surface on the negative electrode current collector (copper foil having a thickness of 10 ⁇ m), dried at 80 ° C. and rolled, and the coating amount on one side is 60 g / m 2 , the mixture density is 1.
  • a negative electrode active material layer of .6 g / cm 3 was formed to prepare a negative electrode precursor.
  • an ionic liquid solution of Li [TFSI] is prepared by dissolving the electrolyte salt in [DEME] [TFSI] so that the concentration of the electrolyte salt is 1.5 mol / L. did.
  • the obtained ionic liquid solution, SiO 2 particles, binder (trade name: Kureha KF Polymer # 8500, Kureha Co., Ltd.), and NMP were mixed in 43 parts by mass, 23 parts by mass, 34 parts by mass, and 143 parts by mass, respectively.
  • a slurry for forming an electrolyte sheet was prepared.
  • This slurry for forming an electrolyte sheet was applied to the main surface on the support film and dried at 80 ° C. to prepare an electrolyte sheet having a thickness of 20 ⁇ m. In order to produce a secondary battery, the obtained electrolyte sheet was punched into a circular shape.
  • Example 2-1 Preparation of positive electrode and negative electrode> Slurry C was added to the positive electrode active material layer of the positive electrode precursor and negative electrode active material layer of the negative electrode precursor produced above by applying a slurry with a gap of 150 ⁇ m by the doctor blade method. Then, the volatile component (dispersion medium) is removed by vacuum drying at 60 ° C. for 12 hours to produce a positive electrode mixture layer and a negative electrode mixture layer. A negative electrode provided was obtained. In order to produce a secondary battery, the obtained positive electrode and negative electrode were punched into a circular shape.
  • a positive electrode, an electrolyte sheet, and a negative electrode punched into a circular shape were stacked in this order and placed in a CR2032-type coin cell container.
  • the obtained laminated body was sealed by caulking the upper part of the battery container via an insulating gasket, to obtain a secondary battery of Example 2-1.
  • Example 2-2 A secondary battery of Example 2-2 was obtained in the same manner as Example 2-1, except that the slurry C was changed to the slurry D.
  • Example 2-3 A secondary battery of Example 2-3 was obtained in the same manner as Example 2-1, except that the slurry C was changed to the slurry E.
  • Example 2-4 A secondary battery of Example 2-4 was obtained in the same manner as Example 2-1, except that the slurry C was changed to the slurry F.
  • Example 2-5 A secondary battery of Example 2-5 was obtained in the same manner as Example 2-1, except that the slurry C was changed to the slurry G.
  • Comparative Example 2-1 A secondary battery of Comparative Example 2-1 was obtained in the same manner as in Example 2-1, except that the slurry C was not applied to the positive electrode active material layer of the positive electrode precursor and the negative electrode active material layer of the negative electrode precursor. .
  • Battery performance was evaluated using the secondary batteries of Examples 2-1 to 2-5 and Comparative Example 2-1 manufactured by the above method.
  • the charge / discharge capacity at 25 ° C. was measured under the following charge / discharge conditions using a charge / discharge device (Toyo System Co., Ltd., trade name: TOSCAT-3200).
  • the results are shown in Table 3. It can be said that the larger the value of the discharge capacity, the better the battery characteristics.
  • the charge capacity and discharge capacity of .05C were determined.
  • the secondary batteries of Examples 2-1 to 2-5 were found to have better battery characteristics than the secondary battery of Comparative Example 2-1. From these results, it was confirmed that the electrode for an electrochemical device of the present invention can enhance battery characteristics even when a battery is produced by adding a solid electrolyte to the electrode mixture layer.
  • This positive electrode active material layer-forming slurry is applied to the main surface of the positive electrode current collector (aluminum foil having a thickness of 20 ⁇ m), dried at 120 ° C., rolled, and coated on one side at 120 g / m 2 .
  • a positive electrode active material layer of 2.7 g / cm 3 was formed to prepare a positive electrode precursor. Then, the electrode was processed for production of a laminate type cell.
  • carbon nanotube conductive agent, trade name: VGCF, fiber diameter 150 nm (manufacturer catalog value), Showa Denko KK) 0.4 part by mass
  • This negative electrode active material layer forming slurry is applied to the main surface on the negative electrode current collector (copper foil having a thickness of 10 ⁇ m), dried at 80 ° C. and rolled, and the coating amount on one side is 60 g / m 2 , the mixture density is 1.
  • a negative electrode active material layer of .6 g / cm 3 was formed to prepare a negative electrode precursor. Then, the electrode was processed for production of a laminate type cell.
  • Li [FSI] is used as an electrolyte salt, and dissolved in [Py13] [FSI] which is an ionic liquid so that the concentration of the electrolyte salt is 1.5 mol / L to prepare an ionic liquid solution of Li [FSI].
  • the obtained ionic liquid solution, SiO 2 particles, binder (trade name: Kureha KF Polymer # 8500, Kureha Co., Ltd.), and NMP were mixed in 43 parts by mass, 23 parts by mass, 34 parts by mass, and 143 parts by mass, respectively.
  • a slurry for forming an electrolyte sheet was prepared. This slurry for forming an electrolyte sheet was applied to the main surface on the support film and dried at 80 ° C. to prepare an electrolyte sheet having a thickness of 20 ⁇ m.
  • Example 3-1 Preparation of positive electrode and negative electrode> Slurry H was added to the positive electrode active material layer of the positive electrode precursor and negative electrode active material layer of the negative electrode precursor produced above by applying a slurry blade with a gap of 150 ⁇ m by the doctor blade method. Then, the volatile component (dispersion medium) is removed by vacuum drying at 60 ° C. for 12 hours to prepare a positive electrode mixture layer and a negative electrode mixture layer, and a positive electrode and a negative electrode mixture layer including the positive electrode mixture layer are provided. A negative electrode was obtained.
  • Example 3-2 A secondary battery of Example 3-2 was obtained in the same manner as Example 3-1, except that the slurry H was changed to the slurry I.
  • Example 3-3 A secondary battery of Example 3-3 was obtained in the same manner as Example 3-1, except that the slurry H was changed to the slurry J.
  • Example 3-4 A secondary battery of Example 3-4 was obtained in the same manner as Example 3-1, except that the slurry H was changed to the slurry K.
  • Battery performance was evaluated using the secondary batteries of Examples 3-1 to 3-4 produced by the above method.
  • the charge / discharge capacity at 25 ° C. was measured at 5 ° C. and 0.05 C using a charge / discharge device (Toyo System Co., Ltd., trade name: TOSCAT-3200).
  • Discharge capacity is a constant current (CCCV) charge at a final voltage of 4.2V and 0.05C, and then a cycle of constant current (CC) discharge to a final voltage of 2.7V at 0.05C.
  • C means “current value (A) / battery capacity (Ah)”.
  • the results are shown in Table 5. It can be said that the larger the value of the discharge capacity, the better the battery characteristics.
  • FIGS. 9 (a) and 9 (b) and FIGS. 10 (a) and 10 (b) show one location of the positive electrode produced in Examples 3-1 to 3-4, which was taken with a scanning electron microscope (SEM). It is a cross-sectional image.
  • the positive electrode includes a positive electrode current collector 30 and a positive electrode mixture layer 20 provided on at least one main surface of the positive electrode current collector 30. From the comparison of the cross-sectional image shown in FIG. 9 and the cross-sectional image shown in FIG. 10, it was observed that the polymer filling property of the positive electrode mixture layer tends to improve as the acetone used in the slurry decreases.
  • the secondary batteries of Examples 3-1 to 3-4 were all excellent in battery characteristics. From these results, it was confirmed that the electrode for an electrochemical device of the present invention can enhance battery characteristics even when a battery is produced by adding a solid electrolyte to the electrode mixture layer. On the other hand, as the mass ratio of the content of the dispersion medium to the content of the polymer becomes smaller, the positive electrode mixture layer can be more fully filled with the polymer, and better ion conductivity tends to be obtained. It was suggested that there is.
  • an electrode for an electrochemical device and a method for producing the same that can improve battery characteristics even when a battery is produced by adding a solid electrolyte to an electrode mixture layer.
  • the electrochemical device using such an electrode for electrochemical devices is provided.
  • the polymer electrolyte composition which can improve the ionic conductivity of an electrode mixture layer is provided.

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Abstract

La présente invention concerne une électrode de dispositif électrochimique comprenant un collecteur de courant, et une couche de mélange d'électrode disposée sur au moins une surface principale du collecteur de courant, la couche de mélange d'électrode comprenant : un matériau actif d'électrode ; un polymère possédant une unité structurale représentée par la formule générale (1) ; au moins un sel d'électrolyte choisi dans le groupe constitué par un sel de lithium, un sel de sodium, un sel de calcium et un sel de magnésium ; et un sel fondu ayant un point de fusion à 250 °C. [Dans la formule (1), X- représente un contre-anion.]
PCT/JP2018/016318 2017-04-21 2018-04-20 Électrode de dispositif électrochimique et son procédé de production, dispositif électrochimique et composition d'électrolyte polymère WO2018194159A1 (fr)

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CN202310599693.XA CN116404107A (zh) 2017-04-21 2018-04-20 电化学装置用电极及电化学装置
US16/606,334 US11462767B2 (en) 2017-04-21 2018-04-20 Electrochemical device electrode. method for producing electrochemical device electrode and electrochemical device
JP2019513702A JP7163909B2 (ja) 2017-04-21 2018-04-20 電気化学デバイス用電極の製造方法
CN201880026140.2A CN110537274B (zh) 2017-04-21 2018-04-20 电极及其制造方法、电化学装置和聚合物电解质组合物
EP18787019.1A EP3614469A4 (fr) 2017-04-21 2018-04-20 Électrode de dispositif électrochimique et son procédé de production, dispositif électrochimique et composition d'électrolyte polymère
KR1020197029920A KR102595311B1 (ko) 2017-04-21 2018-04-20 전기 화학 디바이스용 전극 및 그의 제조 방법, 전기 화학 디바이스, 그리고 폴리머 전해질 조성물

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PCT/JP2017/016084 WO2018193630A1 (fr) 2017-04-21 2017-04-21 Électrode de dispositif électrochimique et dispositif électrochimique
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